Alkylation of paraffin hydrocarbons



March 19, 1946. A. v. GRossE ETAL '2,39%344 ALKYLATION OF PARAFFIN HYDROCARBONS Filed oct. 1-1, 194s a sheets-sheet 1 Nm, g NLNWNQ AI QN n March 19, 1946.y A'. v. GROSSE ETAL 2,396,844

ALKYLATION oF PARAFFIN HYRocARBoNs' Filed Oct. 1l, 1943 l 2 Shee'tS-Sheet I?.

m w Q mw y Patented Mar. 19,1946 y 12,396,844?

UNHTED STATES PATENT OFFICE A t `.2,396,844 ALKYLATIongAIrFFm HYDRO- t Aristid v. Grosse, Haverford, ra., and cari' B. Linn, Riverside, Ill., assignors to Universal Oil Products Company, Chicago, l'll., a corporationl of Delaware r p Application occulter 11, 194s, serial No. 505,786 11 claims'. (o1. 26o-683.4) This application is a continuation-in-part of is gradually-lostby reduction andthe products ofA our oo pending application Serial No. 419,386, tiled the reactions are contaminated with sulfur com- November` 17, 1941, now Patent No. 2,335,507, ispounds and oxidation products. v sued November 30, 1943, which is in turn a con- Phosphoric acid has a limited application but 'tinuation-in-part of application Seri'al No.248,'777, 5 the reactions are not accelerated to a practicalfiled December 31, 1938 and now Pat-ent` No.' degree unless undesirably high temperatures are" 2,267,730 issued December 30, 1941. The presentv employed. Aluminum chloride and similar multil application is also related to our. copending Patvalent metal salts present the usual disadvantages ents Nos. 2,333,648 and 2,333,649, both tiled Octo-v inherent in the use of solid granular catalysts.

ber 28,1941, and issued November 9, 1943. ,l in that the eiciency of the reaction is to some This invention is concerned with the interacextent contingent on the neness of subdivision tion of isoparans or branched chain paraflin hyof the catalyst and that recovery of the active drocarbons containing at -least one tertiary carsalts from their sludges isdiiiicult and expensive. bon-atom per molecule with mono-olenic hydro- The use of boron uoride is not practical on aclcarbons in the presence of catalysts. .15 count of the cost of this compound.

It is more specifically concerned with a simple In the present invention the aforementioned and easily regulated process involving the use diiculties are obviated by the use of a catalyst o1' a liquid catalyst which is only slightly altered whose essential active ingredient is liquid hydroin the course of the reactions and which catagen fluoride. The alkylationproducts which are lyzes the desired reactions' with a maximum of 2*,0 obtained by the interaction of an isoparain with eiciency.

Processes for the formation of higher molecular usually contain relatively minor amounts of alkyl Y weight branched chain hydrocarbons from essenuorides which. are formed during the alkylation branched compounds are of present importance sirable since these compounds may decompose and o engines when hydrocarbons containing alkyl nur 2,2,4-trimethylpentane which forms the standard rides are employed as motor fuels. The presence of reference in rating the antiknock value of gasov of alkyl i'lporides also eiects the lead susceptibillines. Considerable quantities of butanes and buity of the alkylate adversely. Moreover, the for-f tenes are available as by-products from the crackmation of alkyl fluorides represents an appreciable ing of petroleum fraction to produce relatively loss of hydrogen uoridecatalyst. I high primary yields of Vgasoline and by proper 3.5 In a broad aspect the present invention is consegregation of butanes and butenes by solvent ex cerned with the decomposition of -alkyl fluorides material yields of the desired iso-octanesl Efforts a hydrogen uoride catalyst. A to alkylate normal butane with butenes in the 40 In one specic embodiment the invention compresence of catalysts have thus far failed unless prises contacting a hydrocarbon fraction containconcurrent isomerization of the normal butanes to ing relatively minor amounts of an alkyl fluoride iso-butane occurs. However, iso-butane'fractions and produced by the alkylation of an isoparaflin may be made to linteract with butenes and parwith an olen in the presence o1 hydrogen iiuorlde ticularly isobutene in ythe presence of various withadehydroiiuorinating catalyst whereby to decatalysts to form valuable iso-octanes. compose said alkyl uoride to hydrogen uoride Catalysts previously tried to effect the alkyla` and the corresponding olen, reacting the hydrotion of iso-paran hydrocarbonswith oleiin hygen iiuoride thus formed with a metal uoride sedrocarbons include sulfuric acid, phosphoric acid, lected from the group consisting of sodium and v potassium uorides, returning the olen formed which have disadvantages which are in alarge in said dehydroiiuorination step to the alkylation measure overcome by the use of the catalysts of step, 'subsequently recovering hydrogen fluoride the present' invention. sulfuric acid, for example, from its reaction product Vwith said metal fluoride. has atendency to oxidize hydrocarbons with the and returning said recovered hydrogen fluoride formati@ of sulfur dioxide S0 that the catalyst to the alkylationstep.

y ered and reused.

Y eration of this process, the agitation may We have determined that whereas previous work in alkylating various classes of hydrocarbons with oleflns has indicated that the reactions could be brought about in the presence of boron fluoride and minor amounts or hydrogen lfluoride; the reactions are better brought about when us- ,anhydrous hydrogen uoride. This catalyst is a liquid boiling at about jC. so that it can be used in apparatus which is cooled` to maintain temperatures below this point or can be used at higher temperatures if sufiiclent pressures are maintained upon the apparatus. By maintaining an excess of iso-paraiiin at all times, polymerization reactions and the `formation of alkyl iluorides are minimized so that the products consist principally of alkylated derivatives of the original iso-paraflins. The catalyst is not changed by oxidation or reduction and if lost mechanically it can be readily recovk Any 'alkyl uorldes formed are readily decomposable as hereinafter described in greater detail.

In operating the alkylation process, the preferred procedure is to agitato a mixture of liquid hydrogen uoride and an iso-paraffin and gradually introduce a mixture of an olefin and an lso-paraflin below the surface iluoride-iso-paraflln mixture.

of the hydrogen In the batch opbe stopped and the upper hydrocarbon layer fractionated to recover unchanged parafns and the products. Obviously the proc-- desiredalkylated ess may be made continuous by providing a mixing zone in which sufliclent time is given for the completion of the settling zone from which a withdrawn and alkylated products and unconverted isoparafflnfor recycling, whe the lower hydrogen fluoride layer is lpumped back for further service.

For the purpose of illustrating a characteristic apparatus hook-up in which the process may be-conducted, the attached drawings show dialgrammatlcally in general side elevation and by the'use of conventional figures two arrangements of interconnected units suitable for continuous operation. Figure I illustrates one method of conducting the alkylation process per se, while Figure II illustrates one manner in which the present invention may be combined with the alkylation process. It is understood that minor hydrocarbon layer 1s desired reaction followed by a y thence through of receiver- I1 passes through a line i8 containing valve I9 and returned by pump 20 which discharges through line 2| containing valve 22 into line 23 leading to the suction side. of pump 5 so'thatl the hydrogen uoride catalyst is recycled. Another portion of the catalyst may be withdrawn from the system through line I8' and valve` I0' to a regeneration step notshown. l

The hydrocarbon layer in the upper portion through line 24 and valve 25 and enters fractionation column 26 containlng a reboiler 21, unconverted low boiling hydrocarbons being removed as overhead While higher boiling alkylated products of the reaction are withdrawn through line 23 containing valve 20 from the bottom of the column.

The overhead products pass through line containing valve 3| through condenser 32 and rundown line 33 containing a valve 34 to' receiver 35 which has a conventional gas release line 36 containing valve 31 and a liquid draw'line 38 containing valve 39 leading to fractionated to recover desired 40 which may combine features of apparatus construction may be modied without departing essentially from the generally broad scope of the invention. Referring to Figure I, liquid iso-paraffin hydrocarbons may be introduced through line l con-- ity for maintaining the temperature 'of reaction below any desired level while at the same time permitting timefor the completion of the reactions. The reaction products follow line |5.containing valve I5 to a receiver I1 in which 1a separation of hydrogen is effected. The dotted terrace between the hydrogen iluoride is line |1 indicates the intwo phases. A .portion of the withdrawn from the receiver fluoride and hydrocarbons valve |03 to settler ||0 wherein a pump 40 which discharges through line 4 containing valve 42 to storage dinarily through linev 43 containing valve 44 and leading to line 23 to permit tion of the paramns.

The exact temperatures and pressures which should be employed when alkylating various isoparaiiins with various olens will depend upon the activity and physical characteristics of the hydrocarbonsinvolved so that best results will be obtained when conditions are ilrst determined in small scale apparatus. As arule, excessive elevated temperatures are not necessary or desirable and only suilicient pressures should be used to prevent excessive evaporation ofthe catalyst or the hydrocarbons. y

For the recovery for reuse of hydrogen iiuoride with oleiins to form alkyl uorides in the course of the alkylating reactions, these fiuorides may be passed'over granular fluo-- rides such as calcium uoride or aluminum fluorldes which decomposes them into hydrogen uoride and the corresponding -olens. The mixture of olefin and hydrogen uoride is then passed over solid granular sodium or potassium fluoride which forms addition compounds of the type NaF.HF. The oleiin liberated may be recycled for further use and the hydrogen fluoride recovered from the double salt by heating.

Referring to Figure II, an isoparafn-olen feed which may also contain some normal paraiins is introduced by means lnot shown through line |0| containing' valve '|02 to alkylation zone |03. In this case the alkylation zone is depicted as a mechanically agitated zone provided with stirring. device |04 driven by motor |05. Suitable cooling equipment for controlling they reaction temperature may be employed although it is not illustrated in the drawings. Fresh hydrogenfluoride catalyst is added to the through line |06 containing valve |01. The reaction mixture is withdrawn through line |08 and a separation-of catalyst and hydrocarbons 'is effected. The hydrogen fluoride layer is withdrawn through line |35 and a portionthereof may be removed from the system through valve |36 while another portion thereof may be recycled throughA line |31 containing valve |33, pump |39, line |40'containing valve I4|, and line |06.;v v

The. hydrocarbon layer from settler I Il is With-4 drawn through line 4| Il and valve |I2 to pump H3 which discharges through line |I4 omtaininx if desired, but orzone by means not shown.

I containinyalve |34 tion zone.

valve I to fractionator H6. In this column un- 'converted low boiling isoparalns, e. g. lsobutane,

columnl ||6 is withvalve |49 to pump line |5| containing 'Ihe bottoms product from drawn which contains a xed uorination catalyst. drouorinating catalysts which may be employed rination' step is Operated the range of from about 30C.' to about 200 C.,

at a temperature within in the h'ydroand line |06 to the alkyla-l but it will be apparent that the exact temperaoperation, it' will be obvious to those skilled in' the art that variousother techniques of contacting a solid catalyst with uid reactants may be employed.

temperaturev of from about 25 The addition compounds of a'metal uoride such as sodium or potassium u'oride with hydro- Y een uoride are readily decomposed by heating to temperature of 'from about 5 C. to `about '300' C.

zone |61' comprising iso-paraln and dissolved or,

entrained hydrogen uoride is withdrawn through manifold line |68, manifold |86. and valve |88 to line |89 whereby it may berecycled through valve |90 lto line |0`| Sand thence into alkylation zone f :In an alternative meth-od of ,operation the emuy l ent stream .from 'zone |61 may be passed from line |89 through ltne 19|. containing valve |92 to condenser |93 vand thence through line |94 containing 'valve 95 to receiver |96. any hydrogen uoride which is present in excess of the amount soluble in carbon 'layer and the lowerA hydrogen fluoride layer. If non-condensables are present, they may be vented Athrough line |91 containing valve |98. The upper iso-paiain layer is recycled through line |99 and valve 201i to line |11 and then through pump |19 -and the subsequent lines to zone- |61. The lower hydrogen uoride layer may be withdrawn through line 20| containing valve 202 and returned by means of pump 203 through line 20d containing valvev 205 to line |06 and thence into alkylation zone |03. It is preferable, although not essential, to maintain suiiicient pressure on the metal iiuoride containing zone which is undergoing regeneration to maintain the isoparaiiin in substantially the liquid phase in which case the eluent from zone '|61' may be recycled directly through line |89 to the 'alkylation zone as first described. However, in the event that vany substantial portion of the iso-parafn passing through zone |61 is in the vapor phase it will be desirable to divert the eiiluent from said zone through `line |9| to condenser |93 and the subsequent treatment just described.

Itwill, of course, be evidentfthat a fluid other than the unconvertediso-'paraiiin from the alkylatlon step maybe passed through the metal iiuoride zone during regeneration thereof. For example, any suitable uid may be introduced to the regeneration system through line |11 and,

valve |18. 1f the fiuidfemployed is not one which can be introduced into the alkylation zone it will benecessary to divert the effluent stream from the metal fluoride zone undergoing regeneration through line |9| to the condensing and receiving system hereinbefore described.` For example, it may be desirable to pass a relatively inert gas such as nitrogen through the metal fluoride zone undergoing regeneration. This gas introduced through line 4|11 may be heated if desired in zone |02 or it may be by-passed varound said zone through line 208 and'thence-introduced through the manifoidmg system to zone isi. The efnuent stream from zone |91 comprising nitrogen and hydrogen fluoride (the latter being in liquid, va-

.`por, or mixed phase) is withdrawn from the manifolding system through line |89 and line |9| to condenser |93. The non-condensable gas may be separated from receiver |96 through line |99 and valve 200 and thence recycled through line |11,

compressor |19, etc. to zone |61., The condensed hydrogen-iiuoride may be withdrawn from the bottom of receiver |96 through line 20| and recycled to the alkylation zone |09 as 4previously described. y

` Although Figure II as described illustrates a process wherein alkyl uorides are removed from the alkylation products per se, it is within the scope of the invention to treat any hydrocarbon fraction removed from the alkylation process in a similar manner. Thus, in the case oi-certain combination operations it may be desirable to subject the normal butane stream removed from fractionator |53 through line |54 to subsequent hydrocarbon conversion steps such as isomer-ization or dehydrogenation; vIn certain cases this normal butane stream maycontain lower boiling alkyl iiuorides which are not removed with the higher boiling alkylationproducts and which are 'not entirely removed in fractionator H6. In such a case this normal butano stream may be subjected Y to the treatment herein described for decompos-A ingthe alkyl Viluorides and recovering the hydrogen uoride and oleilns. -h

The following experimental data are given by way ofexample to indicate the results obtainable .when alkylating'iso-butane with butemto form iso-octanes.

cause of its commercial importance and it is not to be inferred that the scope-of .the invention is limited in exact'correspondence with lthe data presented.- f

Concentration@ hydrogen juorde To determine whether the anhydrous material 10 and the water solutions of hydrogen iiuoride could equivalent effects, tests were conducted using 100% anhydrous material, a 90% aqueous solution, and a '75% aqueous solution. \An approximately molal equivalent mixture o iso-butano and iso-butene was passed into the 'acids of varying concentration at temperatures from 30 C., the runs being made inia continuously stirred pressure autoclave. Using 100% anhydrous hy 20 drogen uoride, the recovered hydrocarbon layer consisted of Svc-60% octanes of whichabout hal! was 2,2,4-trimethylpentane. The hydrocarbon layer was comp etely saturated and contained only '0.1% of fluo `ne. With the 90% aqueous solution and a molal ratio of paraiiin to oleiin of 1.'5:1, the hydrocarbon layer consisted of 48%' octanes and there was present'1% of ilumine. With a '15% acid solution, an equivalent molal ratio of paraiiin to olefin and a temperature of '30 12 C., no alkylation occurred, but there was considerable formation of butyl iiuorides, iso-butenes forming tertiary butyl iiuoride and normal butenes forming secondary butyl fluorides.

E1Tect of temperature Using a mixture of iso-butano and iso-butene in a molal ratio of 1.521 and 100% hydrogen uoride, best results were obtained at room temperature. At temperatures within the range of -50 40 to -60 C., no alkylation occurred-but there was considerable polymerization of iso-butene. The hydrocarbon layer contained 2% uorine. At a temperature of +90 C. utilizing sufeient pressure to maintain liquid phase and with a paraiinoleflnratio of 1:3, the hydrocarbon products consisted of only 20% octanes and a large amount of more highly alkylated' derivatives. Temperatures as high as 100 C. may be us if desired,fby suitable adjustment of time factor, olen-par ratio, and amount of catalyst used.-

Effect of parain-olen ratio Using a molal ratio of parafiin to olen oi 3:1.

temperatures from 20-30" C. and 100% hydrogen 551 fluoride, 65% of the hydrocarbon-product boiled YWithin the octane range and 50% of this material was 2,2,4trimethyl-.pentane.. The percentand the same temperature and other operating conditions, 50% of thev hydrocarbon prod boiled above 200 C. and contained 510% olen polymers indicating that over-alkylation and polymerization had both taken place.

,weer ofcontact ,time 4 This factor was found to vary with the temperature employed and the reactivity of various iso-paralns and olenns which may be `brought together.

7.0 From theabove data it will be seen that various amounts of alkyl uorldes are found inthe alkylation products dependent primarily upon the operating `conditions in the alkylation step. In

5 any event, amounts of alkyl fluoride on the order of 1.0% o r-iessmay be removed from thealkyia-` This example has been chosen be' tion products by passing the alkylate over a suitable catalyst such as porous calcium iluoride at a temperature of 200 C. The eiliuent mixture is then passed over a granular bed of, sodium uoride at 50 C. whereby the hydrogen fluoride` formed in the dehydrouorination step is substantially completely removed. The bed of sodium fluoride may be subjected to regeneration oride-containing in a subsequent operation by external heating of the bed and passing liquid isoparaflin therethrough to remove the hydrogen fluoride released upon decomposition. This stream of iso-paraflin may then be recycled to the alkylation zone.

We claim as our invention: f

1. In the alkylation of iso-parafiins with olens in the presence of hydrogen fluoride, the improvement whichco'mprises contacting a hydrocarbon fraction containing a relatively minor amount of alkylI fluorides with a dehydrofluorinating catalyst whereby to decompose said alkyl iiuorides' to hydrogen uoride and the corresponding olefi'ns, reacting the hydrogen fluoride thus formed with an alkali metal iluoride to formv an addition compound of the metal fluoride with hydrogen uoride, returning the olen formed in said dehydrofluorination step to the alkylation step, subsequently recovering hydrogen fluoride from .its reaction product withsaid metal fluoride, and returning said recovered hydrogen uoride to the alkylation step.

2. In the alkylation of iso-params with oleilns in the presence of hydrogen uoride, the improvement which comprises contacting a hydrocarbon fraction containing a; relatively minor amount of alkyl fluoride with a dehydroiluorinating catalyst whereby to decompose said alkyl fluorides to hydrogen iiuoriie and the corresponding olens, reacting the hydrogen uoride thus formed with sodium fluoride, returning the olen formed in said dehydrouorination step to the alkylation step, subsequently recovering hydrogen fluoride from its reaction product with said sodium fluoride, and returning said recovered hydrogen uoride tothe alkylation step.

3. The process of claim 1 wherein said hydrogen uoride is recovered by heating the metal uoride-hydrogen uorlde addition compound to decompose said compound and removing the hy-I drogen fluoride thus formed. l

4. The process of claim 1 wherein said hydrogen fluoride is recovered by heating the metal uoride-hydrogen uoride addition compound to decompose said compound, passing an isoparanin through the zone containing said metal fluoride during said heating l fluent stream of iso-paraiin and hydrogen fluoride to the alkylation step. v

step, and returning the efiluoride and the corresponding olens, passing the eiliuent reaction mixture from the dehydrouorination step through a xed bed of a granular alkali metal uoride whereby to form an addition compound between said hydrogen fluoride and said metal fluoride, separating olens from the eiiluent reaction mixture from said metal uzone, returning said separated olens to the alkylation step. subsequently discontinuing the passage of the eiliuent reaction mixture from said dehydrouorination step through said metal fluoride-containing zone, passing a stream of unconverted iso-paraffin separatand olen from a hydrocarbon fraction containing analkyi fluoride, which comprises subjecting, said hydrocarbon fraction to dehydroiuorination to decompose its alkyl iuoride content into hydrogen uoride and olefin, contacting resultant reaction products, containing the hydrogen fluoride and olenn thus formed, with an alkali metal iluoride to form an addition compound of the metal fluoride with the hydrogen fluoride, whereby to separate the latter from the olen. and thereafter decomposing said addition compound to liberate the hydrogen fluoride therefrom.

9. A process for purifying a hydrocarbon fraction containing an alkyl fluoride and for recovering hydrogen fluoride therefrom, which comprises subjecting said hydrocarbon fraction to the action of a dehydrofiuorinating catalyst to decompose its alkyl uoride content into hydrogen uoride and olen, contacting the resultant mixture of hydrocarbons and hydrogen uoride with 5. The process of claim 1 wherein said hydrogen uoride is recovered by passing a substantially inert gas through the zone containing said metal fluoride at a temperature suilicient to decompose the metal fluoride-hydrogen fluoride addition compound, separating hydrogen iluo'ride from the etliuent stream of inert gas and hydrogen uoride, and returning said separated hydrog'en fluoride to the alkylation step.

6. In the alkylationvof isobutane with monoolens -in the presence of a catalyst consisting essentially of hydrogen fluoride, the improvement which comprises contacting a hydrocarbon an alkali metal 'iuoride to form an addition compound of the metal nuoride with the hydrogenv fluoride, whereby to separate the latter from the hydrocarbons, and thereafter heating said addition compound to liberate the hydrogen fluoride therefrom. l

10. A process for purifying a hydrocarbon fraction conta g an alkyl fluoride which comprises subjecting said hydrocarbon fraction to dehydro uorination to decompose the alkyl fluoride into the hydrogen nuoride and thereby separate the latter fromv the hydrocarbons.

11. A process for purifying a hydrocarbon fraction containing an alkyl nuorlde which comprises subjecting said hydrocarbon fraction to the ac- Y .tion of a dehydrouorinating catalyst to decomfraction withdrawn from the alkylation step and containing a relatively minor amount of alkyl iluorides with a dehydroiiuorinating catalyst whereby to decompose said alkyl rluorides to hydrogen pose the alkyl nuoride into hydrogen fluoride and olefin, and contacting the resultant mixture of hydrocarbons and hydrogen nuoride with an alkali metal fluoride to separate the hydrogen ilu'- oride from the hydrocarbons.

ARISTID V. GROSSE. CARL BrLINN. 

